Fungictoal



i Patented July 19,1938

" magma 0.8mm,- rittsbu r'zlxzns jrid cranes, v Q i 'H. Poet, Bristol, Pa assignors toBohm. V jHaas (lompanygul hiladelphiarlarf I No Drawing. Application January 3, 1935, i 'SerialNo.236 i f (Crier-40y This myentionrlateswhen: itseaicides -In copending application Serial: No. 367,626gfiled i May-31, 1929;there la -disclosed anewinsecticide [comprising an organic thiocyanategthe organic residue'of which is aromatic and-contains a nega- I tive' group. In U. S. Patent 1,808,893, there is disclosed a'second type of thiocyanates which are .eflective.insecticides,the organicresidueof which 7 is aliphatic and also contains a negative-group.

10 :Ac'cording to BulletinllBiiipU. S: Dept. of Agriculture, ethyl and-methylthiocya'nates weretried out as fumigants'but their offensive odor, volatility'and irritant action render them unsuited as contact and household insecticides. We have 5found that the higher esters, starting with the butyl ester in contrast to thelower esters, can be employed as contact poisons. The degree of non-volatility necessary in a contact poison begins with the butyl ester and this characteristic is also possessed by the esters above butyl. We have also found that these higher esters do not possess the same offensive odor as the lower esters. ,The thiocyanates described herein are the esters of thiocyanic acidand aliphatic alcohols containing more than three carbon atoms such as the amyl alcohol,capryl alcohol, etc., or of alicyclic alcohols such as, for instance, cyclohexanol. The aliphatic alcohols may be primary, secondaryor tertiary and may have a normal or a branched chain. Among the compounds which have been found efiective as insecticides aren-butyl thiocyanate, nand iso-amyl thiocyanates, tertiary butyl thiocyanate, tertiary amyl thiocyanate, capryl thiocyanate,cyclohexyl thiocyanate, etc. These thiocyanates are substantially insoluble in i V water but may be used in solutions of organic solvents, in mixtures, or in aqueous emulsions provided a suitable emulsifying agent isused. Sodium lauryl sulphate has been found effective as an emulsifying agent and kerosene or similar hydrocarbons are' suitable for solvents. The invention may be illustrated by the following examples but it is not limited to the materials 1 i or the concentrations shown since other solutions 5 or emulsions, or mixtures of thiocyanates may be made within the scope of the appended claims.

Example 1.A 4% solution of n-butylthiocyanate in kerosene was prepared, and 12 cc. of this was sprayed into a chamber according. to the method of fly testing devised by Feet and Grady (Jour. Econ. Entomology 21-598--"625, 1928). After 10 minutes, above 95% of the flies in. the chamber were paralyzed and lying on the'fioor. Of these a large number proved to be dead after 24 hours.

' fluxing temperature for hours.

Exam le 2.An"emulsion the same n-butylthiocyanate was prepared in'the following way:

l-gm'. of sodium lauryl sulphate was dissolved in a 1% liters of water, and tothis was added 3 gms. of m-butylthiocyanate.

The mixture was thoroughlyrshaken until agood emulsion resulted and'was atomized from a spray gunonto Catalpa leaves Example 3.--'I'he same procedure was used as in Example 1-: but replacing the n-butylthiocyanate =by isoamylthiocyanatawith similarresults. Example 4.-..-.Results similar to those obtained in Example 2 may be obtained by replacing the n-butyl thiocyanate with amyl thiocyanate.

Example 5.-The same procedure was used as in .which were'badly infested with aphis.. After 24 ..hours over of the aphis were killed. The

foliage was notlnjured in any way; 10

Example 1, but the n-butyl thiocyanate was replaced by cyclohexylthiocyanate. The results ob- The cyclohexylthiocyanate used in this experiment was obtained by the following method: A mixture of 163 g. of cyclohexyl bromide, g. of sodium thiocyanate, and 750 cc..of ethyl alcohol was stirred at the refluxing temperature for 24 hours. concentration of thefiltrate, and a second filtration. The product decomposed to some extent when distilled. in vacuo. The fraction (35 g.) boiling -135? at 1 mm. gaveasulfur analysis corresponding to that calculated for cyclohexyl thiocyanate.

Example 6.By replacing the n-butyl thiocyanate shown in Example 1 with capryl thiocyanate, similar results are obtained. The capryl thiocyanate employed in this example was prepared by the following method: A stirred reaction mixture consisting of g. of capryl bromide, 58 g. of anhydrous sodium thiocyanate, 50 cc. of n-butyl alcohol and 1 g. of copper powder was heated to 118 for 24 hours. The solid material was flltered and the filtrate concentrated at a reduced pressure. The residue was twice fractionated. The fraction (65 g.) which distilledat 137.5-139/25 mm. gave the correct analysis for capryl thiocyanate.

Example 7.Results similar to those shown in Example 2 may be obtained if the n-butyl thiocyanate is replaced by tertiary amyl thiocyanate.

Example 8.Cetyl thiocyanate was prepared as The salt was removed by filtration, I

follows: A mixture of 50 g. of cetyl bromide, 20 g.

of sodium thiocyanate, 12 g. of ethyl alcohol, and 1 g. of copper dust was stirred and heated at re- The reaction mixture was allowed to cool-and then wasextracted with petroleum ether. The resulting solution was decolorized with carbon and concentrated, giving 43 g. of an oily liquid. The nitrogen analysis showed it was 90% cetyl thiocyanate.

Cetyl thiocyanate, made from cetyl bromide and of a purity above 90%, was emulsified with sodium lauryl sulphate so that the solution contained of the thiocyanate and of sodium lauryl sulphate. This emulsion proved to be an eflective aphicide in that it killed about 90% of chrysanthemum aphis.

Example 9.--Diisobutyl cyclohexylthiocyanate was prepared as follows: Forty grams of 'diisobutyl cyclohexanol prepared by catalytic hydrogenation of diisobutyl phenol was converted into the corresponding bromide by boiling with 150 cc. of 48% hydro-bromic acid for four hours. The organic layer was separated and the bromide purified by distillation. Twenty-one grams o! diisobutyl cyclohexylbromide was in turn converted into diisobutyl cyclohexylthiocyanate by treatment with 10g. of anhydrous sodiumthiocyanate and 1 g. of. copper powder in 10 cc. butyl alcohol at 120 for 15 hours; The thiocyanate was isolated from the reaction mixture and purified by distillation. r

If the cetyl thiocyanate of Example 8 is substituted by diisobutyl cyclohexyl .thiocyanate, the kill of aphls is better than 90% within 24 hours.

It is not necessary that the pure cetyl alcohol be used but use may also be made of the alcohols derived from palmitic acid by hydrogenation, or from spermaceti by hydrogenation or by saponification.

The insecticidal compositions described herein may be used to eliminate fiies and other flying insects as well as creeping and biting insects, such as bed bugs, roaches, ants, etc., from rooms by spraying the insecticides into the air, or onto the insects or they may be ,used on plants 0! various kinds for the purpose of killing sucking and chewing insects without injury to the plant.

It is understood that the examples given are by way of illustration and not limitation. Esters other than those specifically mentioned can be employed so long as they have more than tour carbon atoms. While the principal use of these materials is in insecticidal compositions and ior special use as contact poisons, they are in general useful as fungicides, fumigants and disiniectants.

It is understood that wide deviations are possible without departing from the spirit oi the invention, the scope of which is to be limited only by the. following claims. 1 iwhat' we claim is:

1. As anew compound diisobutyl cyclohexylthiocyanate possessing insecticidal properties.

2. An insecticide comprising a cyclohexyl thiocyanate.

3. The compound cyclohexyl thiocyanate. 4. As a new composition of matter a 07010- hexyl thiocyanate.

5. As a newcomposition of matter an alkyl substituted cyclohexyl thiocyanate.

LEON C. HECKERT. CHARLES H. PEET. 

